Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds

Definitions

• This invention relates to a synthetic resin composition which comprises a blend of a thermoplastic resin, generally a polyester resin, which does not exhibit anisotropy in a molten state and a liquid-crystal polyester resin, more particularly, it relates to a synthetic resin composition which is reduced in delamination and excellent in mechanical properties.
• a liquid-crystal polyester resin capable of forming an anisotropic molten phase is a thermoplastic resin having numerous properties such as high strength, high rigidity, high heat resistance, ease of molding due to high fluidity in a molten state, but accompanied with disadvantages such as anisotropy in mechanical properties, and high cost.
• a thermoplastic resin which does not form an anisotropic molten phase is relatively cheap, and exhibits reduced anisotropy in mechanical properties, but has disadvantages such as poor mechanical properties and poor heat resistance. Therefore, many trials have been made to make the most of the both advantages while making up their disadvantages by mixing and using them.
• the present invention is aimed at providing a resin composition which comprises a liquid-crystal polyester resin exhibiting anisotropy in a molten state, and a thermoplastic resin, generally a polyester, which does not exhibit anisotropy in a molten state, which is reduced in delamination and excellent in mechanical strength.
• the present inventors have studied intensively considering the above problems of a mixture of a thermoplastic resin which does not exhibit anisotropy in a molten state and a liquid-crystal polyester resin. As the results, we have found that a composition which is improved in delamination and also has excellent physical properties such as rigidity and strength can be obtained by using particular silane compound(s) together with said thermoplastic resin and said liquid-crystal polyester resin. We have attained the present invention based on such findings.
• the present invention relates to a synthetic resin composition produced by blending 100 parts by weight of a resin component comprising 1 part by weight to less than 50 parts by weight of a thermoplastic resin (a) which does not exhibit anisotropy in a molten state and more than 50 parts by weight to 99 parts by weight of a liquid-crystal polyester resin (b) capable of forming an anisotropic molten phase with 0.01 to 3.0 parts by weight of at least one silane compound (c) selected from among vinylalkoxysilanes, aminoalkoxysilanes and mercaptoalkoxysilanes.
• a resin component comprising 1 part by weight to less than 50 parts by weight of a thermoplastic resin (a) which does not exhibit anisotropy in a molten state and more than 50 parts by weight to 99 parts by weight of a liquid-crystal polyester resin (b) capable of forming an anisotropic molten phase with 0.01 to 3.0 parts by weight of at least one silane compound (c) selected
• the present invention is a synthetic resin composition produced by blending 100 parts by weight of a resin component comprising (a) 1 part by weight to less than 50 parts by weight of a thermoplastic resin which does not exhibit anisotropy in a molten state and (b) more than 50 parts by weight to 99 parts by weight of a liquid-crystal polyester resin capable of forming an anisotropic molten phase with (c) 0.01 to 3.0 parts by weight of at least one silane compound selected from among vinylalkoxysilanes, aminoalkoxysilanes and mercaptoalkoxysilanes.
• thermoplastic resin (a) used in the present invention may be any conventionally used thermoplastic resin so long as it does not exhibit anisotropy in a molten state, and a thermoplastic resin having at least one selected from the group consisting of ester, amide, imide, urethane, carboxyl, hydroxyl, amino and mercapto in the main chain and/or at the end(s) thereof is preferred because of improved delamination and enhanced mechanical strength of the resin composition.
• a thermoplastic resin having at least one selected from the group consisting of ester, amide, imide, carboxyl, hydroxyl, amino and mercapto in the main chain and/or at the end(s) thereof is more preferred. Further, a thermoplastic resin having at least one of such groups in the main chain or at the end(s) thereof is particularly preferred.
• thermoplastic resins includes, for example, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate; polyamide such as 6-nylon, 66 nylon; polyimide, polyurethane, polyphenylene oxide having hydroxyl group at the end(s) thereof; polysulfone, polyether sulfone, polyether ether ketone, polyoxymethylene, polyphenylene sulfide having mercapto group at the end(s) thereof, polymethyl methacrylate having ester in the main chain, polymethyl acrylate, polyvinyl acetate, etc.
• Copolymers consisting of more than two of the constituent monomers of these resins may be employed. Among them, polyester resins are preferably used.
• a liquid-crystal polyester resin (b) used in the present invention is a melt-processed polyester, which has properties wherein the polymer molecular chains are arranged in a regular parallel alignment in a molten state. Such state wherein the molecules are arranged as described above is often referred to as liquid crystalline state.
• the properties of a molten phase exhibiting anisotropy can be confirmed by the conventional polarization assay utilizing cross polarizers. More specifically, confirmation of anisotropy in a molten phase can be attained by utilizing a Leitz polarization microscope and observing a molten sample mounted on a Leitz hot stage under nitrogen atmosphere at the magnification of x40.
• a liquid-crystal polyester resin (b) used in the present invention exhibits optical anisotropy wherein polarized light penetrates even in a molten static phase when observed between cross polarizers.
• a liquid-crystal polyester resin (b) suitably used in the present invention has a tendency to be substantially insoluble in a general solvent, therefore not suitable for solution processing.
• these polymers as mentioned above, can be readily processed by the conventional melt processing.
• liquid-crystal polyester resin (b) which is used in the present invention and capable of forming an anisotropic molten phase
• aromatic polyester and aromatic polyester amide are preferable.
• polyester partly containing an aromatic polyester and an aromatic polyester amide in the same molecular chain is also one of the preferable examples.
• the particularly preferred liquid-crystal polyester resin (b) includes a liquid-crystal aromatic polyester and a liquid-crystal aromatic polyester amide, containing at least one selected from the group consisting of aromatic hydroxycarboxylic acid, aromatic hydroxylamine, aromatic diamine as its constituents.
• a liquid-crystal aromatic polyester and a liquid-crystal aromatic polyester amide synthesized using these compounds as starting materials are particularly preferred.
• a molecular weight modifier may be used, as necessary, together with the aforementioned components.
• Preferred example of the particular compound constituting a liquid-crystal polyester resin (b) used in the present invention includes, for example, naphthalene compounds such as 2,6-naphthalene dicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and 6-hydroxy-2-naphthoic acid; biphenyl compounds such as 4,4'-diphenyl dicarboxylic acid, 4,4'-dihydroxybiphenyl; para-substituted benzene compounds such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol and p-phenylenediamine; and benzene compounds having substituent(s) on its benzene nucleus in addition to that in para-position (wherein such substituent may be selected from the group consisting of chlorine, bromine, methyl, phenyl, 1-phenylethyl), meta-substituted benz
• X is a group selected from the group consisting of C 1-4 alkylene, alkylidene, a group represented by the formula: -O-, a group represented by the formula:-SO-, a group represented by the formula: - SO 2 -, a group represented by the formula: -S-, a group represented by the formula: -CO-; and in formula (III), Y is a group selected from the group consisting of a group represented by the formula: -(CH 2 )n- (wherein n is 1 to 4), a group represented by the formula: -O(CH 2 ) n O- (wherein n is 1 to 4).
• a liquid-crystal polyester resin (b) used in the present invention may be those having part of a polyalkylene terephthalate or part of a polyalkylene naphthalate which does not form an anisotropic molten phase in the same molecular chain, in addition to the aforementioned constituents.
• Carbon number of the alkylene group in this polyalkylene terephthalate part and the polyalkylene naphthalate part is 2 to 4.
• polyethylene terephthalate is particularly preferred.
• a liquid-crystal aromatic polyester and a liquid-crystal aromatic polyester amide containing one or two or more compound(s) selected from the group comprising naphthalene compound, biphenyl compound, para-substituted benzene compound, among the above constituents, as the essential constituent(s) are more preferable examples of the liquid-crystal polyester resin (b).
• p-substituted benzene compounds p-hydroxybenzoic acid, methylhydroquinone and 1-phenylethylhydroquinone are particularly preferred.
• thermoplastic resin (a) which does not exhibit anisotropy in a molten phase and a liquid-crystal polyester resin (b) capable of forming an anisotropic molten phase are used at such ratio that the liquid-polyester resin (b) should be more than 50 parts by weight to 99 parts by weight in the total 100 parts by weight of the resin.
• the ratio of a thermoplastic resin (a) to a liquid-crystal polyester resin (b) is within the range of the present invention, improvement of strength and modulus of elasticity of the resin composition may be obtained due to the coexisting silane compound (c).
• the matrix in the resin composition is constituted by a liquid-crystal polyester resin (b), resulting in desired physical properties of the resin composition, such as temperature of thermal deformation.
• Silane compounds (c) used in the present invention include, for example one or two or more selected from the group consisting of vinylalkoxysilanes, aminoalkoxysilanes and mercaptoalkoxysilanes.
• Example of vinylalkoxysilanes includes, for example, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane;
• example of aminoalkoxysilanes includes, for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, and example of mercapto
• the amount of silane compounds (c) to be added is 0.01 to 3.0 parts by weight, preferably 0.1 to 1.0 parts by weight based on 100 parts by weight of the resin component comprising the components (a) and (b).
• the amount of silane compound (c) to be added is within the above range, delamination, modulus of elasticity, strength of the resin composition will be improved.
• the synthetic resin composition of the present invention may further contain various kinds of fibrous, powdery or laminar inorganic fillers depending on the purpose of application.
• Example of fibrous fillers includes inorganic fibrous materials such as glass fibers, asbestos fibers, silica fibers, silica-alumina fibers, alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, as well as fibers of metals such as stainless steel, aluminum, titanium, copper, brass.
• inorganic fibrous materials such as glass fibers, asbestos fibers, silica fibers, silica-alumina fibers, alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, as well as fibers of metals such as stainless steel, aluminum, titanium, copper, brass.
• example of powdery fillers includes carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, silicate salts such as calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, wollastonite; metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, alumina; metal sulfate such as calcium carbonate, magnesium carbonate; as well as ferrite, various powdery metals such as silicon carbide, silicon nitride, boron nitride.
• silicate salts such as calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, wollastonite
• metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, alumina
• metal sulfate such as calcium carbonate, magnesium carbonate
• various powdery metals such as silicon carbide, silicon nitride, boron nitride.
• Example of laminar inorganic filler includes mica, glass flake, and foil of various metals.
• one of these inorganic fillers may be used. Alternatively two or more of them may be used.
• a surface finishing agent Depending on the desired physical properties, known inorganic fillers which have been processed with a surface finishing agent can be used.
• surface finishing agents includes functional compounds such as epoxy compounds, isocyanate compounds, titanate compounds, silane compounds.
• the amount of inorganic fillers to be added is preferably 1 to 200 parts by weight, and particularly preferably 1 to 100 parts by weight based on 100 parts by weight of the resin component consisting of the components (a) and (b).
• the synthetic resin composition of the present invention may further contain additives such as heat stabilizer, UV absorber, lubricant; organic compound containing bromine atoms and additives to impart flame retardancy such as antimony trioxide.
• additives such as heat stabilizer, UV absorber, lubricant; organic compound containing bromine atoms and additives to impart flame retardancy such as antimony trioxide.
• Hindered phenol-type stabilizers and phosphorous stabilizers are particularly preferably used in the present invention.
• the synthetic resin composition of the present invention may be conducted to injection molding at the temperature not less than fluidization initiation temperature of a liquid-crystal polyester resin (b) capable of forming an anisotropic molten phase and at the temperature not less than melting point of a thermoplastic resin (a) which does not form anisotropic molten phase under the conventional conditions for injection molding, yielding molded products.
• the resin composition of the present invention is reduced in delamination and excellent in modulus of elasticity and strength.
• Polybuthylene terephthalate-1 (hereinafter abbreviated as PBT-1), liquid-crystal polyester resin-2 (hereinafter abbreviated as LCP-2), phosphite ester-1, and silane compound-1 were respectively weighed as shown in Table 1, and mixed together.
• the mixture obtained was melt kneaded in a biaxial extruder having a screw of 30 mm diameter at a resin temperature (extrusion temperature) of 265°C and pelletized. Subsequently, the pellet was molded into test samples by injection molding at a resin temperature (molding temperature) of 265°C. The resulting test samples were used and flexural strength and flexural modulus thereof were determined according to ASTM D790.
• test samples used for the determination of flexural properties were used to evaluate delamination by the following procedure. That is, adhesive tape was adhered onto the test sample and then peeled it off, then the amount of the removed resin of the surface layer was visually evaluated. The results are expressed as ⁇ , ⁇ , X.
• test samples were prepared in the same manner as that described in Example 1, except that composition of the resin composition was changed as shown in Tables 1 and 2, and the resin temperature during melt kneading and injection molding were those shown in Tables 1 and 2, and the samples were evaluated. The results are shown in Tables 1 and 2.
• Resin compositions were prepared according to the method corresponding to those in Examples 1 to 12, except that silane compound (c) was not added as shown in Tables 1 to 3.
• the test samples were prepared in the same manner as that in Example 1 using the resin composition obtained, and evaluated. The results are shown in Tables 1 to 3.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1995
  • 1995-10-23 JP JP27418595A patent/JPH09111103A/ja active Pending
• 1996
  • 1996-10-22 WO PCT/JP1996/003064 patent/WO1997015628A1/ja not_active Application Discontinuation
  • 1996-10-22 EP EP96935401A patent/EP0857759A4/de not_active Withdrawn

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